Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/48—Polyethers
  • C08G18/4804—Two or more polyethers of different physical or chemical nature
  • C08G18/4816—Two or more polyethers of different physical or chemical nature mixtures of two or more polyetherpolyols having at least three hydroxy groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/16—Catalysts
  • C08G18/22—Catalysts containing metal compounds
  • C08G18/24—Catalysts containing metal compounds of tin
  • C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/48—Polyethers
  • C08G18/4866—Polyethers having a low unsaturation value
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2110/00—Foam properties
  • C08G2110/0008—Foam properties flexible
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2110/00—Foam properties
  • C08G2110/0041—Foam properties having specified density
  • C08G2110/005—< 50kg/m3
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2110/00—Foam properties
  • C08G2110/0083—Foam properties prepared using water as the sole blowing agent

Definitions

• the present invention provides a process for the production of polyurethane foams, in particular flexible polyurethane foams, wherein the resulting polyurethane foams have low emission values and a good resistance to ageing.
• VOC volatile organic constituents
• DE-A 1 121 802 and U.S. Pat. No. 3,397,158 disclose a process for the production of polyurethane foams with the aid of tin(II) salts of carboxylic acids having 1 to 18 carbon atoms, such as tin(II) octoate, tin(II) oleate, tin(II) stearate, tin(II) acetate or tin(II) (2-ethylhexoate).
• tin(II) salts of carboxylic acids having 1 to 18 carbon atoms such as tin(II) octoate, tin(II) oleate, tin(II) stearate, tin(II) acetate or tin(II) (2-ethylhexoate).
• a process is likewise known for the production of polyurethane foams with the aid of the tin(II) salt of ricinoleic acid, Sn(C 18 H 33 O 3 ) 2 , for example Kosmos® EF from Evonik Goldschmidt GmbH, 45127 Essen, Germany.
• the tin catalysts known from the prior art have a number of disadvantages in the production of polyurethane foams, such as high emission or fogging values (e.g. in accordance with VDA 278) and reduced mechanical properties after ageing.
• the object of the present invention is therefore to provide a process which allows the production of polyurethane foams, in particular flexible polyurethane foams, which have both a low emission and a good resistance to ageing (in particular a good level of values for the compression set and the values after ageing in hot air and after ageing in a steam autoclave).
• An emboidment of the present invention is a process for producing a polyurethane foam from
• Another embodiment of the present invention is the above process, wherein said at least one auxiliary substance and/or additive is a catalyst different from component A5, a surface active additive, a pigment, and/or a flameproofing agent.
• Another embodiment of the present invention is the above process, wherein
• B comprises at least one compound selected from the group consisting of 2,4-tolylene-diisocyanate, 2,6-tolylene-diisocyanate, 4,4′-diphenylmethane-diisocyanate, 2,4′-diphenylmethane-diisocyanate, 2,2′-diphenylmethane-diisocyanate, and polyphenyl-polymethylene-polyisocyanate.
• Another embodiment of the present invention is the above process, wherein wherein said is carried out at a characteristic number of from 95 to 125.
• Another embodiment of the present invention is the above process, wherein said process produces a flexible polyurethane foams having an apparent density of from 10 kg m ⁇ 3 to 200 kg m ⁇ 3 .
• A5 comprises a tin(II) salt of a carboxylic acid, wherein said carboxylic acid comprises from 12 to 16 carbon atoms.
• Alb 5 comprises a tin(II) salt of a carboxylic acid having the formula (I)
• x is an integer from 9 to 15; and C x H 2x+1 is a branched carbon chain.
• Another embodiment of the present invention is the above process, wherein x is an integer from 11 to 15.
• A5 comprises the tin(II) salt of 2-butyloctanoic acid.
• A5 comprises the tin(II) salt of 2-hexyldecanoic acid.
• Another embodiment of the present invention is the above process, wherein apart from A5, no further tin(II) salts of carboxylic acids are employed in said process.
• Yet another embodiment of the present invention is a polyurethane foam obtained by the above process.
• This object is achieved by a process for the production of polyurethane foams, preferably for the production of flexible polyurethane foams, from
• the present invention provides in particular a process for the production of polyurethane foams, preferably for the production of flexible polyurethane foams, from
• Component A is a compound having Component A:
• Component B is a compound having Component B:
• isocyanate-based foams are known per se and described e.g. in DE-A 1 694 142, DE-A 1 694 215 and DE-A 1 720 768 and in Kunststoff-Handbuch volume VII, Polyurethane, edited by Vieweg and Höchtlein, Carl Hanser Verlag Kunststoff 1966, and in the revised edition of this book, edited by G. Oertel, Carl Hanser Verlag Kunststoff, Vienna 1993.
• the foams are predominantly foams containing urethane and/or uretdione and/or urea and/or carbodiimide groups.
• the use according to the invention preferably takes place in the production of polyurethane and polyisocyanurate foams.
• Starting components according to component A1 are compounds which have at least two hydrogen atoms which are reactive towards isocyanates and a molecular weight as a rule of 400-15,000. This is understood as meaning, in addition to compounds containing amino groups, thio groups or carboxyl groups, preferably compounds containing hydroxyl groups, in particular compounds containing 2 to 8 hydroxyl groups, specifically those of molecular weight 1,000 to 6,000, preferably 2,000 to 6,000, e.g. polyethers and polyesters as well as polycarbonates and polyester-amides containing at least 2, as a rule 2 to 8, but preferably 2 to 6 hydroxyl groups, such as are known per se for the preparation of homogeneous and of cellular polyurethanes and such as are described e.g. in EP-A 0 007 502, pages 8 - 15.
• the polyethers containing at least two hydroxyl groups are preferred according to the invention.
• Compounds which have at least two hydrogen atoms which are reactive towards isocyanates and a molecular weight of 32 to 399 are optionally employed as component A2. These are to be understood as meaning compounds containing hydroxyl groups and/or amino groups and/or thiol groups and/or carboxyl groups, preferably compounds containing hydroxyl groups and/or amino groups, which serve as chain lengthening agents or crosslinking agents. These compounds as a rule contain 2 to 8, preferably 2 to 4 hydrogen atoms which are reactive towards isocyanates. For example, ethanolamine, diethanolamine, triethanolamine, sorbitol and/or glycerol can be employed as component A2. Further examples of compounds according to component A2 are described in EP-A 0 007 502, pages 16-17.
• Water and/or physical blowing agents are employed as component A3.
• Carbon dioxide and/or highly volatile organic substances as blowing agents are employed, for example, as physical blowing agents.
• component A4 Auxiliary substances and additives are optionally used as component A4, such as
• auxiliary substances and additives which are optionally to be co-used are described, for example, in EP-A 0 000 389, pages 18-21. Further examples of auxiliary substances and additives which are optionally to be co-used according to the invention and details of the mode of use and action of these auxiliary substances and additives are described in Kunststoff-Handbuch , volume VII, edited by G. Oertel, Carl-Hanser-Verlag, Kunststoff, 3rd edition, 1993, e.g. on pages 104-127.
• Catalysts which are preferably employed are: aliphatic tertiary amines (for example trimethylamine, tetramethylbutanediamine, 3-dimethylaminopropylamine, N,N-bis(3-dimethylaminopropyl)-N-isopropanolamine), cycloaliphatic tertiary amines (for example 1,4-diaza(2,2,2)bicyclooctane), aliphatic amino ethers (for example bisdimethylaminoethyl ether, 2-(2-dimethylaminoethoxy)ethanol and N,N,N-trimethyl-N-hydroxyethyl-bisaminoethyl ether), cycloaliphatic amino ethers (for example N-ethylmorpholine), aliphatic amidines, cycloaliphatic amidines, urea and derivatives of urea (such as, for example, aminoalkylureas, see, for
• Tin(II) salts of carboxylic acids are employed as component A5, the particular carboxylic acid on which they are based having from 10 to 16, preferably from 12 to 16 carbon atoms.
• no further tin(II) salts of carboxylic acids are employed in the process according to the invention in addition to component A5.
• x denotes an integer from 9 to 15, preferably from 11 to 15, is employed as component A5.
• the alkyl chain C x H 2x+1 of the carboxylate is a branched carbon chain, i.e. C x H 2x+1 is an iso-alkyl group.
• tin(II) salt of 2-butyloctanoic acid i.e. tin(II) (2-butyloctoate
• tin(II) salt of 2-hexyldecanoic acid i.e. tin(II) (2-hexyldecanoate
• the tin(II) salts according to the invention act as catalysts in the production of polyurethane foam from components A and B.
• the tin(II) salts according to the invention have the technical advantage over the tin(II) salts known from the prior art that they result, with a good processability, in a polyurethane foam which has low emission values (such as, for example, the VOC value measured by the method VDA 278) and has a good resistance to ageing (such as, for example, compression set).
• Aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates such as are described e.g. by W. Siefken in Justus Liebigs Annalen der Chemie, 562, pages 75 to 136 are employed as component B, for example those of the formula (II)
• n 2-4, preferably 2-3, and
• polyisocyanates such as are described in EP-A 0 007 502, pages 7-8.
• Particularly preferred compounds are as a rule the polyisocyanates which are readily accessible industrially, e.g. 2,4- and 2,6-toluylene-diisocyanate and any desired mixtures of these isomers (“TDI”); polyphenyl-polymethylene-polyisocyanates, such as are prepared by aniline-formaldehyde condensation and subsequent phosgenation (“crude MDI”) and polyisocyanates containing carbodiimide groups, urethane groups, allophanate groups, isocyanurate groups, urea groups or biuret groups (“modified polyisocyanates”), in particular those modified polyisocyanates which are derived from 2,4- and/or 2,6-toluylene-diisocyanate or from 4,4′- and/or 2,4′-diphenylmethane-diisocyanate.
• TDI 2,
• At least one compound chosen from the group consisting of 2,4- and 2,6-toluylene-diisocyanate, 4,4′- and 2,4′- and 2,2′-diphenylmethane-diisocyanate and polyphenyl-polymethylene-polyisocyanate (“polynuclear MDI”) is employed as component B.
• the polyurethane foams can be produced by various processes of slabstock foam production or in moulds.
• the reaction components are reacted by the one-stage process which is known per se, the prepolymer process or the semi-prepolymer process, mechanical equipment such as is described in U.S. Pat. No. 2,764,565 preferably being used. Details of processing equipment which is also possible according to the invention are described in Vieweg and Höchtlen (eds.): Kunststoff-Handbuch , volume VII, Carl-Hanser-Verlag, Kunststoff 1966, p. 121 to 205.
• foaming can also be carried out in closed moulds.
• the reaction mixture is introduced into a mould.
• Metal e.g. aluminium, or plastic, e.g. epoxy resin, is possible as the mould material.
• the foamable reaction mixture foams in the mould and forms the shaped article.
• Foam moulding can be carried out in this context such that the moulding has a cell structure on its surface. However, it can also be carried out such that the moulding has a compact skin and a cellular core.
• the procedure can be to introduce foamable reaction mixture into the mould in an amount such that the foam formed just fills the mould.
• the procedure can also be to introduce more foamable reaction mixture into the mould than is necessary to fill in the inside of the mould with foam.
• the production is carried out with so-called “overcharging”; such a procedure is known e.g. from U.S. Pat. No. 3,178,490 and U.S. Pat. No. 3 182 104.
• External release agents which are known per se, such as silicone oils, are often co-used for foam moulding. However, so-called “internal release agents” can also be used, optionally in a mixture with external release agents, such as emerges, for example, from DE-OS 21 21 670 and DE-OS 23 07 589.
• the polyurethane foams are preferably produced by slabstock foaming or by the double conveyor belt process which is known per se (see, for example, “ Kunststoffhandbuch ”, volume VII, Carl Hanser Verlag, Kunststoff Vienna, 3rd edition 1993, p. 148).
• the process according to the invention is used for the production of flexible polyurethane foams with an apparent density (also called bulk density) of from 10 kg m ⁇ 3 to 200 kg m ⁇ 3 , particularly preferably from 15 kg m ⁇ 3 to 80 kg m ⁇ 3 .
• Component A3 Water
• Component B is a compound having Component B:
• the starting components are processed in the one-stage process by means of slabstock foaming under the conventional processing conditions for the production of polyurethane foams.
• Table 1 shows the characteristic number for the processing (the amount of component B to be employed in relation to component A is obtained from this).
• the characteristic number indicates the percentage ratio of the amount of isocyanate actually employed to the stoichiometric, i.e. calculated, amount of isocyanate groups (NCO).
• the bulk density was determined in accordance with DIN EN ISO 845.
• the compressive strength (CLD 40%) was determined in accordance with DIN EN ISO 3386-1-98 at a deformation of 40%, 4th cycle.
• the tensile strength and the elongation at break were determined in accordance with DIN EN ISO 1798.
• the compression set (CS 90%) was determined in accordance with DIN EN ISO 1856-2000 at 90% deformation.
• the compression set (CS 50%) was determined in accordance with DIN EN 1856-2000 (22 h, 70° C.) at 50% deformation.
• the emission values were determined by method VDA 278.
• the catalysts A5-1 (tin(II) salt of 2-butyloctanoic acid) and A5-2 (tin(II) salt of 2-hexyldecanoic acid) according to the invention have the advantage that these are liquid at room temperature and show a good catalytic activity as the catalyst in the production of polyurethane foams.
• the resulting flexible polyurethane foams (Examples 1 and 2 according to the invention) have good mechanical properties and very low VOC values in the emission test according to VDA 278.
• component A5-5 When the tin(II) salt of oleic acid (component A5-5) is employed as component A5 in the recipes of Table 1, this leads to unusable polyurethane foams because the reaction mixture does not set during the production.
• Table 2 illustrate the mechanical properties also after ageing of the flexible polyurethane foams which were produced with the catalysts A5-1 (tin(II) salt of 2-butyloctanoic acid) and A5-2 (tin(II) salt of 2-hexyldecanoic acid) according to the invention (Examples 5 and 6 according to the invention): It was found, surprisingly, that the polyurethane foams produced with the aid of the tin(II) salts A5-1 and A5-2 according to the invention achieve the level of mechanical values of polyurethane foams produced with the tin(II) salt of 2-ethylhexanoic acid. As shown with the aid of the above in Table 1, however, the polyurethane foams produced with the tin(II) salts according to the invention have the additional advantage that they have significantly lower emission values.

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